JPH07309957A - Polyarylene sulfide resin molding excellent in surface property - Google Patents

Abstract

PURPOSE:To obtain a polyarylene sulfide resin molding excellent in surface property by molding a composition obtained by melt-kneading a mixture of a polyarylene sulfide resin with an amide polymer and a filler by bringing it in a melt state into contact with a metallic surface at a specified temperature. CONSTITUTION:A composition obtained by melt-kneading a mixture of 100 pts.wt. polyarylene sulfide resin with 0.3-10 pts.wt. polymer having at least one group selected from among amide, imide and amino and 0-300 pts.wt. filler and being in a melt state is brought into contact with a metallic surface at a surface temperature of 85-130 deg.C to form a molding. The critical surface tension of this molding is to be 25N/m or above. It is desirable that the temperature of the metallic surface with which the composition in a melt state is brought into contact falls within the range of 90-110 deg.C. It is desirable that the above composition further contains 0.05-3 pts.wt. alkoxysilane such as vinylalkoxysilane or epoxysilane per 100 pts.wt. polyarylene sulfide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin molded article having improved surface characteristics. More specifically, a composition having a polymer having a specific functional group mixed with a polyarylene sulfide resin is formed by contacting with a metal surface at a specific temperature, and the adhesiveness, paintability, printability, and adhesion are characterized. To a polyarylene sulfide resin molded article excellent in

[0002]

2. Description of the Related Art In recent years,
Electric and electronic equipment parts materials, automobile equipment parts materials, chemical equipment parts materials, and other functional parts materials are required to have high heat resistance, chemical resistance, and flame retardant thermoplastic resin. There is. Polyarylene sulfide resins typified by polyphenylene sulfide are also one of the resins that meet this demand, and the demand for them is increasing due to their good cost-to-cost ratio. However, polyarylene sulfide resin has chemical resistance, heat resistance, combustion resistance,
Although it has excellent mechanical strength, it lacks adhesiveness with adhesives, paints, and inks, so it is easy to peel off even if the molded product is adhered with an adhesive, and the coating film and printed characters are easily peeled off even if painting or printing is applied. It has drawbacks and has limited use in these applications. As a method for improving the adhesiveness of a paint or the like to the surface of a molded article, for example, a graft or block copolymer having an affinity with the polyarylene sulfide resin and having an affinity with the paint or the like is added to the polyarylene sulfide resin. The method (Japanese Patent Laid-Open No. 61-200166) has been proposed, but it is not sufficient yet, and further improvement in adhesiveness is desired. On the other hand, polyarylene sulfide resin molded products for insert molding of metal parts have already been used for applications such as switches and coil bobbins. In these applications, it is necessary to improve the adhesion between the metal and the resin in order to suppress the infiltration of cleaning agents and water at the interface between the resin and the metal, but depending on the application, sufficient adhesion can still be obtained. However, further improvement is desired.

[0003]

SUMMARY OF THE INVENTION In view of the present situation, the inventors of the present invention have made diligent studies to improve the adhesiveness and adhesion of polyarylene sulfide resin molded products, and have investigated surface characteristics of polyarylene sulfide resin molded products. As a result of studying the modification method, a polymer having a specific functional group was blended with a polyarylene sulfide resin, melt-kneaded, and molded by bringing it into contact with a metal surface at a specific temperature, thereby improving the critical surface tension of the molded product. It has been found that a practically molded product excellent in adhesiveness and adhesiveness can be provided by setting it to 25 N / m or more, and the present invention has been completed. That is, the present invention is
(A) 100 parts by weight of polyarylene sulfide resin,
(B) 0.3 to 10 parts by weight of a polymer having at least one of an amide group, an imide group and an amino group, and (C) 0 to a filler.
A composition obtained by blending 300 parts by weight and melt-kneading and molding in contact with a metal surface having a surface temperature in the range of 85 to 130 ° C. in a molten state has a critical surface tension of 25 N.
/ M or more and is a polyarylene sulfide resin molded article having excellent surface characteristics.

First, each component of the resin composition used for producing the resin molded article of the present invention will be described. The polyarylene sulfide resin as the component (A) used in the present invention is mainly composed of a repeating unit-(-Ar-S)-(where Ar is an arylene group). Examples of the arylene group (-Ar-) include p-phenylene group, m-phenylene group, o-phenylene group, and substituted phenylene group (provided that the substituent is an alkyl group, preferably a C _{1 to} C ₅ alkyl group, or (Phenyl group), p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'-diphenylene ether group, p, p'-diphenylenecarbonyl group, naphthalene group and the like can be used. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, a polymer using the same repeating unit, that is, a homopolymer may be used, and from the viewpoint of processability of the composition, a different repeating unit. In some cases, copolymers containing are preferred. As the homopolymer, a substantially linear polymer having a repeating unit of a p-phenylene sulfide group using a p-phenylene group as an arylene group is particularly preferably used.
Further, as the copolymer, a combination of two or more different arylene sulfide groups consisting of the above-mentioned arylene groups can be used, but among them, a combination mainly containing a p-phenylene sulfide group and containing an m-phenylene sulfide group is preferable. Particularly preferably used. In this,
A substantially linear product containing 60 mol% or more, and more preferably 70 mol% or more of p-phenylene sulfide group has heat resistance,
It is suitable from the viewpoint of physical properties such as moldability and mechanical properties.
Further, the copolymer containing m-phenylene sulfide group in an amount of 5 to 40 mol%, particularly 10 to 25 mol%, is preferable. In this case, the repeating units of the components are contained in a block form rather than a random form (for example, JP-A-61-1422).
The material described in Japanese Patent No. 8) has good workability, heat resistance, and mechanical properties and can be preferably used. The polyarylene sulfide resin as the component (A) used in the present invention is a linear polymer having a relatively low molecular weight, or it is oxidatively or thermally crosslinked to increase the melt viscosity (molecular weight) and improve the moldability. Although the above polymers can be used, it is also possible to use a high molecular weight polymer having a substantially linear structure obtained by polycondensation from a monomer mainly composed of a bifunctional monomer. In terms of physical properties of the obtained molded product, the latter substantially linear structure polymer is more preferable in many cases. Further, as the polyarylene sulfide resin of the present invention, in addition to the above-mentioned polymer, a branched or crosslinked polyarylene sulfide resin obtained by mixing and using a monomer having three or more functional groups as a part of the monomer or a polymer thereof It is also possible to use a compounded resin in which the above-mentioned linear polymer is blended, which is preferable.

In order to produce a polyarylene sulfide resin molded article having excellent adhesiveness and adhesion according to the present invention, a polyarylene sulfide resin is prepared by adding at least one of an amide group, an imide group and an amino group as the component (B). It is characterized in that a polymer having a group is blended and melt-kneaded to form a resin composition. Examples of the component (B) include polyamide resins, polyimide resins, polyamine resins and the like. Examples of polyamide resins include nylon 4,
6, Nylon 6,6, Nylon 6, Nylon 12, Aromatic polyamide, Polyacrylamide, etc. can be used, heat resistance,
In terms of affinity, nylon 4,6, nylon 6,6 and aromatic polyamide are preferred. Examples of the polyimide-based resin include polyimide, polyamide-imide, and polyether-imide. For example, Vespel manufactured by DuPont, Upimol R, Upimol S manufactured by Ube Industries, and New- manufactured by Mitsui Toatsu Co., Ltd.
TPI, Torlon manufactured by Amoco, Ultem manufactured by Engineering Plastics, Kinel manufactured by Nippon Polyimide Co., Kelimide, and the like are commercially available, and these polyimide resins can be used. As the polyamine resin, for example, melamine resin, polyvinylamine, polyethyleneimine, polyallylamine and the like can be used, and melamine resin is preferable. The blending amount of the component (B) is 0.3 to 10 with respect to 100 parts by weight of the polyarylene sulfide resin as the component (A).
If it is too small, the desired adhesiveness and adhesion will be insufficient.On the other hand, if it exceeds 10 parts by weight, the characteristics that the polyarylene sulfide resin originally possesses will differ depending on the type of component (B). It is not preferable because it may be damaged.

Next, the filler as the component (C) used in the present invention is not always an essential component, but a molded article excellent in performance such as mechanical strength, heat resistance, dimensional stability, and electrical properties is required. In order to obtain it, it is preferable to mix. For this purpose, a fibrous, powdery, plate-like, or hollow filler is used depending on the purpose. As the fibrous filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber,
Examples thereof include boron fibers, potassium titanate fibers, and inorganic fibrous substances such as metal fibrous substances such as stainless steel, aluminum, titanium, copper, and brass. As a granular filler,
Carbon black, silica, quartz powder, glass beads,
Glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron oxide, titanium oxide, alumina, carbonic acid of metals such as calcium carbonate, magnesium carbonate. Examples thereof include salts, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of the plate-like filler include mica, glass flakes, various metal foils and the like. or,
Examples of the hollow filler include glass balloons and shirasu balloons. These fillers can be used alone or in combination of two or more. The compounding amount of the filler is 4 parts with respect to 100 parts by weight of the polyarylene sulfide resin as the component (A).
It is less than 00 parts by weight, and if it is more than this, moldability and
It is not preferable because it deteriorates toughness. It is particularly preferably 250 parts by weight or less.

The alkoxysilane which is the component (D) used in the present invention is not always an essential component, but it is preferably blended in order to improve the toughness of the molded product and to suppress burrs generated during injection molding. The alkoxysilane is one or more of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and allylalkoxysilane. Examples of vinylalkoxysilanes include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy) silane. Examples of epoxyalkoxysilanes include γ-glycidoxypropyltrimethoxysilane and β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like, examples of aminoalkoxysilanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-aminopropylmethyldiethoxy. Silane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.,
Examples of the mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and examples of the allylalkoxysilane include γ-diallylaminopropyltrimethoxysilane, γ-allylaminopropyltrimethoxysilane and γ. -Allylthiopropyltrimethoxysilane and the like. The compounding amount of the alkoxysilane as the component (D) is 0.05 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin [component (A)].

The polyarylene sulfide resin composition used for producing the molded article of the present invention can be prepared by various known methods, but at least the above-mentioned components (A) and (B),
And, if necessary, melt by heating in the coexistence of the components (C) and (D),
It is necessary to perform melt-kneading treatment for 30 seconds or more. Specifically, for example, (A), (B), (C) and (D) components are mixed in advance with a mixer such as a tumbler or a Henschel mixer,
It is supplied to a uniaxial or biaxial extruder and melt-kneaded. The kneading temperature is 10 ° C to 1 ° C below the melting temperature of the resin component.
The temperature is 00 ° C. higher, preferably 10 ° C. to 60 ° C. higher. If the temperature is too high, the resin may be decomposed or an abnormal reaction may be caused, which is not preferable. The kneading treatment time varies depending on the treatment temperature and the type and blending amount of each component, but is at least 30 seconds or more and 15 minutes or less, preferably 1 minute or more and 10 minutes or less. The kneaded product thus produced may be directly molded in the molten state, or may be formed into pellets in advance and then subjected to molding.

The polyarylene sulfide resin molded article having excellent adhesiveness and adhesion according to the present invention has a critical surface tension of 25 N when the above kneaded product is brought into contact with a metal surface at a specific temperature in a molten state. It is characterized in that it is molded so as to be / m. The critical surface tension is usually measured by the Zisman plot method (J. Colloid Sci., 5, 514, 19
50) applies. To briefly describe this method, the contact angles (θ) of several liquids were measured on the surface of the molded product, and the relationship between the liquid surface tension (γ) and each cosθ was plotted.
The surface tension at the point where the line connecting each point and the line cos θ = 1 intersect can be obtained as the critical surface tension (γ _c ).

The molding method may be any molding method suitable for molding a desired shape, and examples thereof include an injection molding method, an extrusion molding method, a melt compression molding method and an injection compression molding method. As the kind of metal that comes into contact with the molten resin composition, any metal can be used as long as it does not hinder the molding of the molded product. For example, mold steel, stainless steel,
Examples include aluminum, copper, iron, silver, gold and the like. Regarding the contact method with the metal surface, when good adhesiveness between the surface of the molded product and the paint, adhesive, or ink is required, for example, in injection molding or melt compression molding, a resin composition in a molten state on the mold surface In the extrusion molding, the molten resin composition may pass through a metal die or nozzle. When adhesion with metal parts is required, for example, the metal parts are installed in advance inside the mold during injection molding, and the molten resin composition and the metal parts are brought into contact with each other during injection molding. Good. The temperature of the metal surface to be contacted varies depending on the molding method suitable for obtaining a molded product having a target shape, but is usually 140 ° C to 150 ° C which is lower than the crystallization temperature of the resin composition.
Molded at a temperature of ℃, sufficient adhesiveness can be obtained even in this temperature range, but if better adhesiveness is required, if the temperature of the metal surface is within the range of 85 to 130 ℃, It is preferable because good adhesiveness with paints, adhesives and inks can be obtained. For example, in the case of injection molding, when the mold temperature is molded in the range of 85 to 130 ° C, preferably 90 to 110 ° C, good adhesiveness between the molded product and the adhesive is obtained without significantly impairing the appearance of the molded product. Is obtained. If the mold temperature is lower than 85 ° C, the appearance of the molded product may be deteriorated, which is not preferable, though it depends on the molding method and molding conditions. The resin temperature during molding is 10 ° C. to 60 ° C. higher than the melting point of the resin. If the temperature is set too high, the resin is decomposed to cause deposits on the metal surface, which is not preferable. Other molding conditions may be set according to the molding method and the shape of the molded product. Regarding the effect of improving the adhesiveness and adhesiveness of the polyarylene sulfide resin molded article of the present invention, a detailed mechanism has not been clarified, but a polymer having an amide group, an imide group, and an amino group in the polyarylene sulfide resin is used. By blending and melt-kneading, a highly polar functional group effective in improving adhesiveness and adhesion is generated in the polyarylene sulfide resin or the composition thereof, and a metal surface at a specific temperature in a molten state It is speculated that the functional groups efficiently appeared at the interface between the metal surface and the resin by contact, and the adhesiveness and adhesion were improved.

The composition used in the present invention contains an antioxidant, a heat stabilizer, a lubricant, and a lubricant within a range not departing from the object of the present invention.
A crystal nucleating agent, an ultraviolet absorber, a colorant, a release agent, and other usual additives can be added. It is also possible to supplementarily add a small amount of another thermoplastic resin.

[0012]

As is apparent from the above description and examples, the polyarylene sulfide resin molded product of the present invention can be used as an adhesive, a paint, and a resin composition without impairing the mechanical properties of the molded product.
It has the effect of improving the adhesion to ink and the like and the effect of improving the adhesion to metal parts.

[0013]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Examples 1 to 6 and Comparative Examples 1 and 2 Polyphenylene sulfide resin (melting point 285 ° C., 310
C., melt viscosity measured at a shear rate of 1200 sec ^-1 500 poise) 100 parts by weight of nylon 6,6 and optionally glass fiber (glass fiber diameter 10 μm, chopped strand 3 mm long) and γ-aminopropyltri Ethoxysilane was blended in the ratio shown in Table 1 and premixed for 5 minutes with a Henschel mixer. This was melt-kneaded with an extruder having a cylinder temperature of 320 ° C. (residence time of about 2 minutes) to prepare pellets of the polyphenylene sulfide resin composition shown in Table 1.
Next, using an injection molding machine, the cylinder temperature is 320 ° C and the mold temperature is 1
ASTM tensile test pieces were molded under the conditions of 30 ° C., and a tensile test and an adhesive strength test were performed. The adhesive strength was determined by the following method. Cut an ASTM tensile test piece at half the length and thoroughly wash it with acetone,
Then, it was adhered using an epoxy adhesive (Konishi Pond E30H manufactured by Konishi Co., Ltd.). After the adhesion, it was cured at 120 ° C. for 1 hour, and then left for 1 day in an atmosphere of 23 ° C. and a humidity of 50% to conduct a tensile test to determine the shear adhesive strength. Also, AS
The critical surface tension was determined by the Zisman plot method (J. Colloid Sci., 5, 514, 1950) using a TM tensile test piece. On the other hand, the adhesion of the metal part inserted into the polyphenylene sulfide resin molded product was evaluated as the ink penetration distance by the following method. Set the metal lead frame in the mold with the injection molding machine and set the cylinder temperature to 320
A test piece into which a lead frame as shown in FIGS. One terminal side of this test piece was immersed in a specific fluorescent ink (PEP fluorescent penetrant F-6A-SP manufactured by Eishin Chemical Co., Ltd.) to a depth of half of the test piece for 15 minutes at room temperature to cause capillary phenomenon. The adhesion between the metal and the resin was evaluated by the ink penetration distance (X in FIG. 4) that penetrated between the metal lead frame and the resin. The measurable ink penetration distance is 14 mm. Further, the surface appearance of the test piece was visually evaluated. The results are summarized in Table 1.

Examples 7 to 14 (B) As components (B), pellets of the polyphenylene sulfide resin composition shown in Table 2 were prepared in the same manner as in Examples 2 and 5 except that various polymers shown in Table 2 were used. Similar evaluation was performed. The results are summarized in Table 2.

Examples 15 to 16 and Comparative Examples 3 to 4 Using the pellets of the polyarylene sulfide resin composition of Example 6, an injection molding machine was used at a cylinder temperature of 320 ° C. and at a mold temperature shown in Table 3 at ASTM. A tensile test piece was molded, and an adhesive strength test and a critical surface tension measurement were performed in the same manner as in Example 6. Further, the surface appearance of the test piece was visually evaluated. The results are summarized in Table 3.

Examples 17-18, Comparative Examples 5-6 Using the pellets of the polyarylene sulfide resin composition of Example 2, an adhesive strength test was conducted in the same manner as in Examples 15-16 and Comparative Examples 3-4. The critical surface tension was measured and the surface appearance was evaluated. The results are summarized in Table 4.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[Brief description of drawings]

FIG. 1 is a plan view of an example of a molded part into which a lead frame of the present invention is inserted.

FIG. 2 is a side view of an example of a molded part into which the lead frame of the present invention is inserted.

FIG. 3 is a front view of an example of a molded part into which the lead frame of the present invention is inserted.

FIG. 4 is a partially enlarged view of FIG. 1 showing a measurement part of an ink penetration test in an example.

[Explanation of symbols]

 1 Lead frame (made of copper) [black part in the drawing] 2 Resin part [hatched part in the drawing] 3 Lead frame terminal 4 Gate part 5 Ink penetration test measuring part X Ink penetration distance

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Claims (3)

[Claims] 1. An (A) polyarylene sulfide resin 1
0.3 to 10 parts by weight of (B) a polymer having at least one of an amide group, an imide group and an amino group, and (C)
The critical surface of a molded product, which is obtained by molding a composition prepared by mixing 0 to 300 parts by weight of a filler and melt-kneading it in contact with a metal surface having a surface temperature in the range of 85 to 130 ° C in a molten state. A polyarylene sulfide resin molded product with a tension of 25 N / m or more and excellent surface properties. 2. The resin molded article according to claim 1, wherein the temperature of the metal surface with which the composition is brought into contact in a molten state is in the range of 90 to 110 ° C. 3. The composition further comprises (D) vinylalkoxysilane based on 100 parts by weight of polyarylene sulfide,
Epoxyalkoxysilane, aminoalkoxysilane,
The resin molded product according to claim 1 or 2, which comprises 0.05 to 3 parts by weight of at least one alkoxysilane compound selected from the group consisting of mercaptoalkoxysilane and allylalkoxysilane.